Ether diisocyanates

ABSTRACT

WHERE N IS 4 TO 19, M IS 0 TO 15, THE SUM OF N AND M IS 13 TO 19, R1, R2 and R3 are hydrogen or short chain alkyl groups of one to four carbon atoms and R is a monovalent organic radical. Polymers prepared from such diisocyanates and organic compounds containing active hydrogens.   Ether diisocyanates of the formulas:

United States Patent Kuder et al.

[ 51 Sept. 12,1972

[54] ETHER DIISOCYANATES [72] Inventors: Robert C. Kuder, Excelsior,Minn. 55331; Marwan R. Kama], Dhahran, Saudi Arabia [73] Assignee:General Mills, Inc.

[22] Filed: April 25, 1969 [21] App1.No.: 819,496

[52] US. Cl ..260/453 AR, 260/77.5 AT, 260/453 AR, 260/465 [51] Int. Cl..C07e 119/04 [58] Field of Search ..260/453 AL, 453 AR [56] ReferencesCited UNITED STATES PATENTS 3,144,468 8/1964 Hoover et al ..260/453Primary Examiner-Joseph Rebold Assistant Examiner-C. F. WarrenAttorney-Anthony A. Juettner, William C. Babcock and Gene 0. Enockson[57] ABSTRACT Ether diisocyanates of the formulas:

and

8 Claims, No Drawings ETHER DIISOCYANATES The present invention relatesto new ether diisocyanates. More particularly, it relates to suchdiisocyanates derived from diamines prepared by hydrogenating dinitrilesultimately obtained from monohydroxy compounds, certain fatty compoundsand unsaturated nitriles. It also relates to polymers prepared from theether diisocyanates and organic compounds containing two or more activehydrogens.

The new diisocyanates of the present invention have the structuralformulas:

and

wherenis4to l9,m isOto l5,the sum ofnandm is 13 to 19, R R and R arehydrogen or short chain alkyl groups of one to four carbon atoms and Ris a monovalent organic radical. The sum of the whole integers m and nis preferably 15. R,'-R are preferably hydrogen and R is preferably amonovalent hydrocarbon radical of one to about 20 carbon atoms. Our newdiisocyanates can be reacted with a wide variety of active hydrogencontaining compounds to produce polymers including polyurethanes,polyureas, and the like. Such polymers are useful as coatings, sealants,adhesives, etc.

The diisocyanates of the invention are prepared by the reaction of thecorresponding diamines with phosgene. In turn, the diamines are preparedby the hydrogenation of dinitriles. The said dinitriles are prepared bythe reaction of a monohydroxy compound with an epoxy substituted fattynitrile, followed by the reaction of the resulting product with ana,,B-unsaturated nitrile. Representative a,B-unsaturated nitriles areacrylonitrile, methacrylonitrile and crotononitrile with the first beingthe preferred reactant.

The starting epoxy substituted fatty nitriles can be prepared in anumber of known ways from monoethylenically unsaturated fatty nitrilesof 16 to 22 carbon atoms. The preparation of the nitriles from thecorresponding fatty acids and ammonia is also well known. Thispreparation and the conditions useful in the same are setforth in FattyAcids And Their Derivatives by A. W. Ralston, 1948, pp. 620-625 (JohnWiley & Sons, lnc.). The useful monoethylenically unsaturated aliphaticmonobasic carboxylic acids which can be converted to the mono-nitrilesand then to the starting epoxy substituted mono-nitriles can berepresented by the following:

9-hexadecenoic (palmitoleic), 7-hexadecenoic, 2-

hexadecenoic, Z-heptadeconoic, 2-octadecenoic, 3-octadecenoic,4-octadecenoic, fi-octadecenoic, 6-octadecenoic (petroselinic),7-octadecenoic, 8- octadecenoic, 9-octadecenoic (oleic, elaidic), l-

octadecenoic, l l-octadecenoic (vaccenic), l2-octadecenoic,2-nonadecenoic, 9-eicosenoic (gadoleic), ll-eicosenoic, 13-docosenoic(erucic), ll-docosenoic (cetoleic), and the like. The oxidation of themono-nitriles to the epoxy substituted nitriles is readily accomplishedwith mild oxidizing agents, preferably peracetic acid. The epoxysubstituted nitriles can also be prepared according to the procedure ofU.S. Pat. No. 2,756,242. The epoxy substituted fatty nitrile is thenconverted to an ether and hydroxy substituted nitrile by reaction with amonohydroxy compound. Such reaction (or etherification) is preferablycarried out in the presence of an acid catalyst. Sulfuric acid isonepreferred catalyst. A wide variety of monohydroxy compounds can beutilized. Representative of such are: aliphatic alcohols includingmethanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol,octanol, 2- ethylhexanol, nonanol, decanol, dodecanol, hexadecanol,octadecanol, and the like; phenols such as phenol, p-nonyl phenol,o-cresol, other alkyl substituted phenols and the like; cycloaliphaticalcohols such as cyclohexanol, and alkyl substituted cyclohexanols, andaryl substituted aliphatic alcohols such as benzyl alcohol, and alkylsubstituted benzyl alcohols.

The alkyl substituents on the various classes of alcohols and phenolscan be branched or straight chained and preferably contain from one to12 carbon atoms. The monohydroxy compounds can also contain inertsubstituents such as C1, nitro and the like but it is preferred that theresulting R group be unsubstituted hydrocarbon. The preferredmonohydroxy compounds are the saturated aliphatic alcohols of one toabout 18 carbon atoms.

The a,B-unsaturated nitrile is condensed with the described ether andhydroxy substituted nitriles using an alkaline catalyst and moderatetemperatures. A preferred catalyst is sodium ethoxide prepared bydissolving sodium in absolute ethanol. It is also preferred to use anexcess of the unsaturated nitrile and temperatures of about 25 to C. arepreferred. The resulting product comprises a mixture of.'positionisomers which can be separated if desired by chromatography and thelike. However, there is ordinarily no reason to do so since thecompounds are functionally equivalent.

The described dinitriles are then converted to diamines byhydrogenation. The hydrogenation is carried out in the presence ofammonia utilizing a hydrogenation catalyst such as Raney cobalt or Raneynickel. I

The diamines are converted to the diisocyanates of the present inventionby the conventional procedure of reacting phosgene therewith and thendecomposing the intermediate carbamyl chlorides by raising the reactiontemperature. The reaction is preferably carried out in an organicsolvent such as toluene.

The following Examples A-F are illustrative of the preparation of thedinitriles without being limiting.

EXAMPLE A A mixture of 279 g. of 9,10-epoxystearonitrile, 1,000 ml. ofmethanol, and 2 g. of concentrated sulfuric acid was refluxed for twohours. About 600 ml. of the methanol was then distilled off, and theremainder of the reaction mixture was poured into water. The oil layerwas taken up in hexane, the hexane extract washed with salt water, andthe hexane stripped off on a rotary evaporator, leaving 298 g. crudemethoxyhydroxystearonitrile. On vacuum-distillation of the 5 crudeproduct, 82 percent was obtained as a light yellow liquid boiling atl60t4 C. at 0.07 mm. Hg.

To 145 g. of the above distilled methoxyhydroxystearonitrile were added2 ml. of sodium ethoxide catalyst solution (made by dissolving 0.5 g.sodium in g. absolute alcohol) and 20.6 g. acrylonitrile. The mixturewas held at about 60 C. for 3 hours. Then another 2 ml. catalystsolution and 21.8 g. acrylonitrile were added and heating was continuedat about 60 C. for another 3 hours. The reaction mixture was thendiluted with hexane, filtered and washed to remove the catalyst.Evaporation of the hexane left l6l g. crudemethoxy-(cyanoethoxy)-stearonitrile. On vacuumdistillation of the crudeproduct, 69 percent was ob tained as a yellow liquid boiling mostly atl80-l90 C. at 0.08 mm. Hg. and containing 7.50 percent nitrogen. Theproduct comprised a mixture of 9-methoxy-lO-(B-cyanoethoxy)stearonitrile and l0-methoxy-9-(B- cyanoethoxy)stearonitrilehaving the formulas:

II it N OCll Cll cm and ll ll CHZCI'IZC N EXAMPLE BButoxy-(cyanoethoxy)-stearonitrile was prepared in essentially the samemanner as set forth in Example A using n-butanol in place of methanol.The product comprised a mixture of9-butoxy-IO-(B-cyanoethoxy)stearonitrile andlO-butoxy-9-(,B-cyanoethoxy)stearonitrile having the formulas:

NECCIIZCHQ CIIzCIIgCIIgCIIg 0113011 015011 on orrgozN EXAMPLE C tll ttlllflll EXAMPLE D Cetyloxy-(cyanoethoxy)-stearonitrile was prepared inessentially the same manner as set forth in Example A using cetylalcohol (n-hexadecyl alcohol) in place of methanol. The productcomprised a mixture of 9- ypalmitonitrile. The resulting9-methoxy-l0-(B- cyanoethoxy)-palmitonitrile and l0-methoxy-9-(B-cyanoethoxy)-palmitonitrile have the formulas:

Example A is essentially repeated using phenol in place of methanol. Theresulting 9-phenoxy-l0-(B- cyanoethoxy)-stearonitrile andl0phenoxy-9-(B- cyanoethoxy)-stearonitrile have the formulas:

II H

H II l N C CHzCIIz and The following examples are illustrative of thepreparation of the diamines without being limiting.

EXAMPLE G A mixture of 175 g. distilledmethoxy-(cyanoethoxy)-stearonitrile as prepared in Example A, 175 g.methanol, 26.5 g. Raney cobalt catalyst, and I50 ml. liquid ammonia washeated at l45l50 C. in a stirred autoclave under a pressure of 860-1550psi of hydrogen until uptake of hydrogen ceased (about 3 hours). Thecatalyst was then filtered off and the am-' monia and methanol strippedout under vacuum, leaving 174 g. crude methoxy-(aminopropoxy)-stearylamine. On vacuum distillation of the crude product, 95 percent wasobtained as a colorless liquid boiling mostly at l7080 C. at 0.2 mm. Hg,with a nitrogen content of 6.94 percent and an amine number of 282. Theproduct comprised a mixture of 9-methoxy-lO-(yaminopropoxy)-stearylamine and l-methoxy-9-(yamino-propoxy)-stearyl amine having theformulas:

Such mixture of position isomers can be separated (as well as theisomers of the examples to follow) such as by chromatography. However,there is ordinarily no reason to do so since the compounds arefunctionally equivalent.

EXAMPLE H Example G was essentially repeated using the dinitrile ofExample B. The resulting product comprised a mixture of9-butoxy-lO-(y-aminopropoxy} stearyl amine andl0-butoxy-9-(y-aminopropoxy)- stearyl amine having the formulas:

ll 11 CH3-(CH1)1-dJd)(CHg)1CH NHg 5 8 inNou-lomcug ougcugougcui H and ll11 (lll;t(Cll2)7-( -d1((lllg)7CllgNllg EXAMPLE J Example G wasessentially repeated using the dinitrile of Example C. The resultingproduct comprised a mixture of 9-octyloxy-lO-(y-aminopropoxy)- stearylamine and lO-octyloxy9-('y-aminopropoxy)- stearyl amine having theformulas:

and

II II and u ll

EXAMPLE L Example G is essentially repeated using the dinitrile ofExample E. The resulting product comprises a mixture of9-methoxy-l0-(y-aminopropoxy)-palmityl amine andlO-methoxy-9-(y-aminopropoxy)-palmityl amine having the formulas:

Example G is essentially repeated using the dinitrile of Example F. Theresulting product comprises a mixture of9-phenoxy-l0-(y-aminopropoxy)-stearyl amine andlO-phenoxy-9-('y-aminopropoxy)-stearyl amine having the formulas: (Le.

The following examples are illustrative of the preparation of thediisocyanates of the invention without being limiting.

and

EXAMPLEl and A solution of 100 g. distilledmethoxy-(yaminopropoxyl)-stearyl amine as prepared in Example CIl(ClI:)r$-$(CIl:)r 2N G in 200 g. dry toluene was added over a 60 minute5 o 0 period to a solution of 397 g. phosgene in 800 g. dry mmcumcfig\twhumcugmwo toluene. The temperature of the reaction mixture increasedfrom to 30 C. during this time. The tem- EXAMPLE lV 32:23" y ii sgggifgi 33 g gla iii ag; Example I was essentially repeated using thediamine l0 returned to the reaction mixture by means of a reflux f i gComprlse? f condenser. The excess phosgene was then removed by F8 g i eedry blowing the reaction mixture with a stream of nitrogen f f i i affi while raising the temperature to 110 C. About one- Steary lsocymnedvmgt e Ormu half of the toluene was then distilled off at atmospheric15 u pressure and the rest removed under vacuum in a rotary evaporator,leaving 10] g. crude methoxy-(iso- CII (C"2)7 cyanato-propoxy)-stearylisocyanate. On distilling the crude product through a falling filmmolecular still 80 OCNCIIQCIIQCIIQ CTIKCIIQHCIIE percent was collectedas distillate (N 1.461) at and jacket temperatures of l50-200 C. and apressure of 11 II about 0.2 mm. Hg. The product was a mixture of 9- d 10m thoxy 9( isocyanatopropoxy) stearyl iso an e ycyanate having theformulas: 5 Ulihmnumco 11 Ill EXAMPLE V l a( )1- I3(CH2)1-CHQNC 0Example I IS essentially repeated using the diamine of OCNCI-I:ClIzC1hO0-011, Example L. The resulting product comprises a mixture and n H of9-methoxy-lO-(y-isocyanatopropoxy)-palmityl isocyanate and10-methoxy-9-(y-isocyanatopropoxy)-pall l -7 c1n co (011) f (OIL) Nmltyl isocyanate havmg the formulas:

C1I3-O 0c1r2o1rgcr-nNco 1 1 1'1 Such mixture of position isomers can beseparated (as CH3 (CII2)5CC(C2)7-CH2NCO well as the isomers of theexamples to follow) such as by chromatography. However, there isordinarily no OCNCilzCliaClIz om reason to do so since the compounds arefunctionally equivalent. and u it EXAMPLE H 40 Clh-(CII)5+-+(CII2)1CIIgNCO Example I was essentially repeated using the diamineof Example H. The resulting product comprised a mix- CIhCHZCHQNCO tureof 9-butox -l0- -isoc anato ro ox -stear 1 isocyanate and l0 butox;-9-('y-isocglan oprogoxy)- EXAMPLE VI stearyl isocyanate having the formas: Example I is essentially repeated using the diamine of H H ExampleM. The resulting product comprises a mixture C P MW A MP N of9-phenoxy-lO-(y-rsocyanatopropoxy)-stearyl isocyanate andl0-phenoxy-9-(y-isocyanatopropoxy)- and ()CNCllgCll2Cll-g0 ()("H2(il:CH2( Hll stearyl isocyanate having the formulas;

11 ll (111 o11:)=(:-(|w crmworrnvco ouacmcilgom-o (Purim-rigours] 0o(llhl(lllfi v$fil(c1191431121")O 0 0 EXAMPLEllI ()(YNCH CIM fl: ExampleI was essentially repeated using the diamine of Example J. The resultingproduct comprised a mixture of9-octyloxy-lO-(y-isocyanatopropoxy)-stearyl isocyanate andlO-octyloxy-9-(y-isocyanatopropoxy)- stearyl isocyanate having theformulas:

As indicated above, our new diisocyanates are par- I 3( 2)7 f 2)7ticularly valuable for the preparation of polymers by reaction withcompounds bearing at least two active ()(NUllgCll-gPlI-z (Ma urity-stilthydrogen atoms as determined by the Zerewitinoff method. TheZerewitinoff test is described by Kohler in J. Am. Chem. Soc., 49, 3181(1927). Such polymers are useful especially as coatings for a variety ofsubstrates.

In general, the active hydrogen atoms of compounds reactive with our newdiisocyanates are attached to carbon, oxygen, nitrogen or sulfur atoms.Compounds containing the following groups will have active hydrogenatoms: primary amino, secondary amino, carboxyl, diazoamino, hydrozino,hydrozo, hydrozono, hydroxyamino, hydroxyl imido, imino and mercapto.Most often these active hydrogen atoms are attached to oxygen, nitrogen,or sulfur atoms; thus they will be a part ofgroups such as OH, SH, NH-,NH CO H, CONH CONHR where R represents an organic radical, -SO OH, SO NHand CSNH Examples of suitable types of compounds include water, hydrogensulfide, ammonia, hydroxyl polyesters, polyhydric polyalkylene ethers,polyhydric polythioethers, polyacetals, aliphatic polyols, includingalkane, alkene and alkyne diols, triols, tetrols and the like, aliphaticthiols including alkane, alkene and alkyne thios having two or more SHgroups; polyamines including both aromatic, aliphatic and heterocyclicdiamines, triamine, tetramines and the like; as well as mixturesthereof. Of course, compounds which contain two or more different groupswithin the above-defined classes may also be used in accordance with thepresent invention such as, for example, amino alcohols which contain anamino group and a hydroxyl group, amino alcohols which contain two aminogroups and one hydroxyl group, aminoacids and the like. Furtherillustrative classes and specific organic compounds containing activehydrogen atoms useful for preparing polymers according to our inventionare described immediately hereinbelow.

Any suitable polyester may be used and may contain terminal hydroxylgroups, terminal carboxylic acid groups, amino groups or the like.Moreover, the polyester may be a polyester amide which was prepared bycondensing an amino alcohol containing both free amino groups and freehydroxyl groups with the other components used in the preparation ofpolyesters. The polyester may be prepared by reacting a polycarboxylicacid or hydroxy carboxylic acid with polyhydric alcohols. It is alsopossible to use a mixture of polyhydric alcohols and polyamines such asethylenediamine, polyethylenediamine, l,4-butylenediamine and the like.Amines such as bis-(2-aminoethyl)ether or amino carboxylic acids such asglycine, alanien, valine, phenylalanine, hydroxyproline and the like mayalso be used. The polyesters may contain hetero atoms in addition to theester groups including oxygen, sulfur, nitrogen and the like in thechain. Moreover, the radicals making up the polyester may be eithersaturated or unsaturated and may contain double or triple bonds as wellas modifying radicals of saturated or unsaturated fatty acids such asoleic acid or fatty alcohols such as aleyl alcohol and the like.

Any suitable polycarboxylic acid may be used in the preparation of thepolyesters such as, for example, oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaicacid, sebacic acid, brassylic acid, maleic acid, fumaric acid,glutaconic acid, alpha-hydromuconic acid, betahydromuconic acid,alpha-butyl-alpha-ethyl-glutaric acid, alpha,beta-diethyl-succinic acid,isophthalic acid,

terephthalic acid, hemimellitic acid, trimellitic acid, tremesic acid,mellophanic acid, prehnitic acid, pyromellitic acid,benzenepentacarboxylic acid, 1,4-

cyclohexanedicarboxylic acid, and the like. Any suita- Any suitablepolyhydric polyalkylene ether may be used as the active hydrogencontaining compound such as, for example, the condensation product of analkylene oxide or of an alkylene oxide with a polyhydric alcohol. Anysuitable polyhydric alcohol may be used such as those disclosed abovefor use in the preparation of the hydroxyl polyesters. Any suitablealkylene oxide may be used such as, for example, ethylene oxide,propylene oxide, butylene oxide, amylene oxide, and the like. Of course,the polyhydric polyalkylene ethers can be prepared from other startingmaterials such as, for example, tetrahydrofuran, epihalohydrins such as,for example, epichlorohydrin and the like as well as aralkylene oxidessuch as, for example, styrene oxide and the like. The polyhydricpolyalkylene ethers may have either primary or secondary hydroxyl groupsand preferably are polyhydric polyalkylene ethers prepared from alkyleneoxides having from two to five carbon atoms such as, for example,polyethylene ether glycols, polypropylene ether glycols, polybutyleneether glycols and the like. It is often advantageous to employ sometrihydric or higher polyhydric alcohols such as glycerine,trimethylolpropane, pentaerythritol and the like in the preparation ofthe polyhydric polyalkylene ethers so that some branching exists in theproduct. Generally speaking, it is advantageous to condense from aboutfive to about 30 moles of alkylene oxide per functional group of thetrihydric or higher polyhydric alcohol. The polyhydric polyalkyleneethers may be prepared by any known process such as, for example, theprocess disclosed in 1859 by Wurtz and in Encyclopedia of ChemicalTechnology, Volume 7, pages 257 to 262, published by lntersciencePublishers, Inc. I951), orin U.S. Pat. No. 1,922,459.

Any suitable polyhydric polythioether may be used such as, for example,the condensation product of thiodiglycol or the reaction product of apolyhydric alcohol such as is disclosed above for the preparation of thehydroxyl polyesters with any other suitable thioether glycol. Othersuitable polyhydric polythioethers are disclosed in U.S. Pat. Nos.2,862,972 and 2,900,368.

Any suitable polyhydric alcohol may be used as the active hydrogencontaining compound such as, for example, alkane diols such as, forexample, ethylene glycol, l,3-propylene glycol, l,2-propylene glycol,l,4- butylene glycol, l,3-butylene glycol, l,5-pentanediol,l,4-butanediol, l,3-pentanediol, l,6-hexanediol, l,7- heptanediol,2,2-dimethyl-l,3-propanediol, l,8-octanediol and the like includingl,20-eicosanediol and the like; alkene diols such as, for example,Z-butenerninc'a 1,4-diol, 2-pentene-l,5-diol, 2-hexene-l,6-diol,2-heptene-l ,7-diol and the like; alkyne diols such as, for example,2-butyne-l,4-diol, 1,5-hexadiyne-l,6-diol and the like; alkane triolssuch as, for example, 1,3,6-hexanetriol, 1,3,7-heptane triol,1,4,8-octane triol, 1,6,12- dodecane triol and the like; alkene triolssuch as 4-hexene-l ,3,6-triol and the like; alkyne triols such as2-hexyne-l,4,6-triol and the like; alkane tetrols such as, for

example, l,2,5,6-hexane tetrol and the like; alkene tetrols such as, forexample, 3-heptene-l,2,6,7-tetrol' and the like; alkyne tetrols such as,for example, 4-octynel ,2,7,8-tetrol and the like.

Any suitable aliphatic thiol including alkane thiols containing two ormore SH groups may be used such as, for example, 1,2-ethane dithiol,l,2-propane dithiol, 1,3-propane dithiol, 1,6-hexane dithiol,1,3,6-hexane trithiol and the like; alkene thiols such as for'example,Z-butene-l ,4-dithiol and the like; alkyne thiols such as, for example,3-hexyne-l ,6-dithiol and the like.

Any suitable polyamine may be used including, for example, aromaticpolyamines such as, for example, pamino aniline, 1,5-diaminonaphthalene, 2,4- diaminotoluene, 1,3,5-benzene triamine, 1,2,3- benzenetriamine, l,4,5,8-naphthalene tetramine and the like; aliphaticpolyamines such as, for example, ethylenediamine, 1,3-propylenediamine,l,4-butylenediamine, 1,3-butylenediamine, diethylenetriamine,triethylenetetramine, 1,3,6-hexane triamine, l,3,5,7-heptane tetramineand the like; heterocyclic polyamines such as for example, 2,6- diaminopyridine, 2,4-diamino-5aminomethyl pyrimidine,2,5-diamino-1,3,4-thiadiazole, piperazine and the like.

One especially preferred group of amines useful for preparing polymersaccording to our invention are polyamines having the primary aminegroups thereof blocked by ketimine or aldimine groups. The reaction ofcarbonyl compounds with the primary amine groups can be illustrated asfollows:

+ H2O T The useful carbonyl compounds may have the following theoreticalstructural formula:

where R and R are organic radicals, are each substantially inert to theketimine or aldimine formation reaction and are preferably hydrogen orshort chain alkyl or ketones that are volatile so that an unreactedexcess thereof may easily be removed by conventional distillationpractices when the reaction is completed. Such volatile compounds arealso preferred so that when the blocked polyamine is mixed with the newdiisocyanate and exposed to moisture, the freed aldehyde or ketone canbe easily removed from the reaction mixture. Examples of preferredcarbonyl compounds include such aldehydes and ketones as acetone, methylethyl ketone, methyl n-butyl ketone, methyl tert-butyl ketone, ethylisopropyl ketone, acetaldehyde, propionaldehyde, butyraldehyde,isobutyraldehyde, and the like i.e., including hexanone and hexanal).The polyamines to be blocked preferably have the structure where R is adifunctional aliphatic group containing from two to 48 carbon atoms, Ris an aliphatic group containing one to 24 carbon atoms and n is aninteger of from 0-20. Representative R radicals are methyl, propyl,butyl, decyl, hexadecyl, hexenyl octenyl, tridecenyl, octadecyl,undecynyl and the like. lnert or non-interfering groups such as C1,nitro and the like may be present on R and/or R Any suitable reactionproduct of a phenol with an alkylene oxide yielding a compoundcontaining active hydrogens may be used such as, for example, thosedisclosed in US. Pat. No. 2,843,568, such as for example, the reactionproduct of hydroquinone with ethylene oxide to give a polyalkylenearylene ether glycol having a molecular weight above about 750 or otherpolyalkylene arylene ether glycols disclosed in said patent.

Any suitable reaction product of a phenol-aldehyde resin with analkylene oxide may be used such as, for example, a novolac having theformula OH O H C H2 l 0 Ha I \/l W h RX R R u R (I) II diamine such as4,4'-diaminodiphenylmethane or the like, xylylene diamine, as well asalkylene diamines such as, for example, ethylenediamine,propylenediamine, 1,4-butylenediamine, hexamethylenediamine and the likeincluding 1,10-

dodecane diamine.

Any suitable phenol may be used such as, for example, 2,2bis(p-hydroxyphenyl)propane (Bisphenol A) and the like.

Any suitable polyamide may be used such as, for example, those obtainedby reacting adipic acid with hexamethylenediamine and the like.

Any suitable polyacetal may be used such as, for example, the reactionproduct of formaldehyde or other suitable aldehydes with a polyhydricalcohol such as those disclosed above for use in the preparation of thehydroxyl polyester.

Other alcohol compounds which do not necessarily fit within any of thepreviously set forth classes of compounds and which nevertheless containactive hydrogen containing groups which are quite suitable for theproduction of the polymers of the present invention are pentaerythritol,sorbitol, triethanolamine, mannitol,N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, as well as compoundsof any of the classes set forth above which are substituted with halogensuch as, for example, chloro, iodo, bromo and the like; nitro; alkoxy,such as, for example, methoxy, ethoxy, propoxy, butoxy and the like;carbo-alkoxy such as for example, carbomethoxy, carboethoxy and thelike; dialkyl amino such as, for example, dimethylamino, diethyl amino,dipropylamino, methylethylamino and the like; mercapto, carbonyl,thiocarbonyl, phosphory], phosphato and the like.

Other substances which can be used include natural substances such ascastor oil and the like.

The molar proportions of the diisocyanate of our invention and thecompounds bearing Zerewitinoff active hydrogen atoms can vary widely.Those skilled in the art can determine the proportions of reactants bestsuited for a particular purpose. For example, when making polyurethaneelastomers, one often uses approximately equimolar amounts of glycol andthe new diisocyanate. Preferably, the active hydrogen containingcompound will be used in a molar ratio to the new diisocyanate of 1:10to 10:1.

The polymers of our invention can be prepared by reacting the newdiisocyanate and the active hydrogen containing compound atsubatmospheric, atmospheric or superatmospheric pressure. Atmosphericpressure is preferred. The reaction can be operated over a wide range oftemperatures. Those skilled in the art will recognize that there aregreat differences in the relative reactivity of various groupscontaining active hydrogen atoms, amines reacting faster than alcohols,primary alcohols reacting faster than tertiary alcohols-to name a fewexamples; accordingly, one will select a temperature at which thereaction occurs at a rate convenient for the purpose at hand.Preferably, the reaction temperature ranges between about 20 and 150 C.However, the temperature is not critical.

If desired, the reaction may be carried out in an inert solvent.Representative solvents include tetrahydrofuran, o-dichlorobenzene,chlorobenzene, xylene, methyl isobutyl ketone, toluene and ethylacetate. In general, the solvent should be free fromisocyanate-reactable groups such as groups bearing Zerewitinoff-activehydrogen atoms.

In the preparation of polymers according to our invention, a portion ofthe new diisocyanates (i.e. up to about 90 mole and preferably from 0 to50 mole can be replaced by known polyisocyanates. Representative of suchknown polyisocyanates are ethylenediisocyanate,hexamethylenediisocyanate, butylene-l,3- diisocyanate, ethylidenediisocyanate, butylidene diisocyanate, 1,2,4-butanetriisocyanate,1,3,3-pentanetriisocyanate, p-phenylene-2,2-bis(ethylisocyanate),1,4-naphthalene-2,2-bis(ethylisocyanate), S-chlorophenylene-l,3-bis(propyl-3-isocyanate), tolylene diisocyanate,m-phenylene diisocyanate, pphenylene diisocyanate,diphenylene-4,4'-diisocyanate, xylylene-l,4-diisocyanate,4,4-diphenylenemethanediisocyanate and the like. A particularlydesirable group of polyisocyanates to be employed in combination withour new diisocyanates in the preparation of the polymers of theinvention are those described in the application of Rogier and Kamal,Serial No. 250,211, filed Jan. 9, 1963, entitled Polyisocyanates andDerivatives. These polyisocyanates are derived from polymeric fat acidsand have the following idealized structural formula:

where y is 0 or 1, x is an integer of 2 to about 4 and R is thehydrocarbon group of polymeric fat acids. Preferably, x is 2. Thepolyisocyanates of the above formula wherein y is 0 are prepared byconverting the polymeric fat acids to the corresponding polymeric acidchlorides, reacting the acid chlorides with a metal azide to form thepolymeric acyl azides and then heating the acyl azides to produce thepolyisocyanates. The polyisocyanates wherein y is l are prepared byconverting the polymeric fat acids to the corresponding EXAMPLE VIl Amixture of 2.00 g. of the diisocyanate as prepared in Example I and 0.77g. of the diketimine prepared from diethylene triamine andmethylisobutyl ketone was spread on a glass plate with a three-mildrawdown bar. The coating dried to a tack-free state in about four hoursat F. and 50 percent relative humidity. It was of good appearance.

EXAMPLES Vlll-Xll Coatings are prepared as in Example Vll using thediisocyanates of Examples Il-Vl. Similar results are obtained. Wheredesired, elevated temperatures and/or catalysts such as dibutyl tindilaurate can be used to accelerate the cure of the polymers of theinvention.

sive property or privilege is claimed are defined as follows:

l. A diisocyanate selected from the group consisting of and mixturesthereof where n is 4 to 19, m is 0 to 15, the sum of n and m is 13 to19, R R and R are hydrogen or alkyl groups of one to four carbon atomsand R is a monovalent hydrocarbon radical of one to about 20 carbonatoms.

2. The diisocyanate of claim 1 wherein R,, R and R are hydrogen.

3. The diisocyanate of claim 1 wherein the sum of n and m is 15.

4. The diisocyanate of claim 1 wherein R R and R5, are hydrogen and thesum of n and m is 15.

5. The diisocyanate of claim 4 wherein n is 8, m is 7 and R is methyl.

6. The diisocyanate of claim 1 wherein n is 8, m is 7 and R is CH (CH CH7. The diisocyanate of claim 1 wherein n is 8, m is 7 and R iSCH2(CH2)14CH3.

8. The diisocyanate of claim 1 wherein n is 8, m is 7 and R is phenyl.

2. The diisocyanate of claim 1 wherein R1, R2 and R3 are hydrogen. 3.The diisocyanate of claim 1 wherein the sum of n and m is
 15. 4. Thediisocyanate of claim 1 wherein R1, R2 and R3 are hydrogen and the sumof n and m is
 15. 5. The diisocyanate of claim 4 wherein n is 8, m is 7and R is methyl.
 6. The diisocyanate of claim 1 wherein n is 8, m is 7and R is -CH2(CH2)6CH3.
 7. The diisocyanate of claim 1 wherein n is 8, mis 7 and R is -CH2(CH2)14CH3.
 8. The diisocyanate of claim 1 wherein nis 8, m is 7 and R is phenyl.